Biological Studies of Chalcogenolato-Bridged Dinuclear Half-Sandwich Complexes
Biological Studies of Chalcogenolato-Bridged Dinuclear Half-Sandwich Complexes
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DOI：
10.1021/ic4022307
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发表时间：
2013-12-02
影响因子：
4.6
通讯作者：
Therrien, Bruno
中科院分区：
文献类型：
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作者：
Johnpeter, Justin P.;Gupta, Gajendra;Therrien, Bruno
由（eta（6）-p-MeC 6 H4 Pri）（2）Ru-2（mu-Cl）（2）Cl-2与（E = S，1; E = Se，2; E = Te，3）分别在乙醇、苯乙醚、苯硒酚和碲酚钠中反应，合成了一系列阳离子硫族根桥联双钌配合物[（eta（6）-p-MeC 6 H4 Pri）（2）Ru-2（mu-EC 6 H5）（3）]（+）.硫醇根合和硒代衍生物以良好的产率分离为氯化物盐，而碲酸根合类似物以六氟磷酸盐分离。类似地，双核五甲基双（C5 Me 5）铑和铱配合物（eta（5）-C5 Me 5）（2）M-2（μ-Cl）（2）Cl-2与苯乙基醚、苯硒醇和碲酚钠在乙醇中反应，得到相应的通式为eta（5）-C5 Me 5）（2）M-2的阳离子双核配合物（μ-EC6H5）（3）]（+）（M = Rh，E = S，4; E = Se，5; E = Te，6; M = Ir，E = S，7; E = Se，8; E = Te，9）。此外，还合成了具有混合硫代硒代桥和硫代碲代桥的阳离子双核配合物[（eta（6）-p-MeC 6 H4 Pri）（2）Ru-2（mu-EC6H5）（mu-SCH2C6H4-p-Bu-t）（2）]（+）（E = Se，10; E = Te，11）和[（eta（5）-C5Me5）（2）M-2（mu-EC6H5）（mu-SCH2C6H5）（2）]（+）（M = Rh，E = Se，12; E = Te，13; M = Ir，E = Se，14; E = Te，15），从中性双核配合物（eta（6）-p-MeC 6 H4 Pri）（2）Ru 2Cl 2（mu-SCH 2C 6 H4-p-Bu-t）（2）和（eta（5）-C5 Me 5）（2）M2-Cl-2（mu-SCH 2C 6 HO 2.所有复合物都具有高度细胞毒性，显示出亚微摩尔范围内的活性。硫族桥的性质似乎对活性有影响，而金属中心的性质起次要作用。在测试的配合物中，具有硫醇桥的双核配合物1、4和7显示出对癌细胞的最高活性和对CT-DNA的最佳亲和力，如细胞生物学和生物物理实验所证明的。
A series of cationic chalcogenolato-bridged diruthenium complexes [(eta(6)-p-MeC6H4Pri)(2)Ru-2(mu-EC6H5)(3)](+) from the reaction of (eta(6)-p-MeC6H4Pri)(2)Ru-2(mu-Cl)(2)Cl-2 with (E = S, 1; E = Se, 2; E = Te, 3) has been obtained in ethanol benzenethiol, benzeneselenol, and sodium tellurophenolate, respectively. The thiolato and selenolato derivatives are isolated in good yield as the chloride salts, while the tellurolato analogue is isolated as the hexafluorophosphate salt. Similarly, the dinuclear pentamethylcyclopentadienyl (C5Me5) rhodium and iridium complexes (eta(5)-C5Me5)(2)M-2(mu-Cl)(2)Cl-2 react with benzenethiol, benzeneselenol, and sodium tellurophenolate in ethanol to give the corresponding cationic dinuclear complexes of the general formula eta(5)-C5Me5)(2)M-2(mu-EC6H5)(3)](+) (M = Rh, E = S, 4; E = Se, 5; E = Te, 6; M = Ir, E = S, 7; E = Se, 8; E = Te, 9). In addition, cationic dinuclear complexes with mixed thiolatoselenolato and thiolato-tellurolato bridges have been prepared, [(eta(6)-p-MeC6H4Pri)(2)Ru-2(mu-EC6H5)(mu-SCH2C6H4-p-Bu-t)(2)](+) (E = Se, 10; E = Te, 11) and [(eta(5)-C5Me5)(2)M-2(mu-EC6H5)(mu-SCH2C6H5)(2)](+) (M = Rh, E = Se, 12; E = Te, 13; M = Ir, E = Se, 14; E = Te, 15), starting from the neutral dinuclear complexes (eta(6)-p-MeC6H4Pri)(2)Ru2Cl2(mu-SCH2C6H4-p-Bu-t)(2) and (eta(5)-C5Me5)(2)M-2-Cl-2(mu-SCH2C6HO2. All complexes are highly cytotoxic showing activity in the submicromolar range. The nature of the chalcogenolato bridges seems to have an impact on the activity, while the nature of the metal center plays a minor role. Among the complexes tested, the dinuclear complexes 1, 4, and 7 with the thiolato bridges show the highest activity on cancer cells and the best affinity for CT-DNA as demonstrated by cell biology and biophysical experiments.